WO2011118486A1 - 分離膜およびその製造方法 - Google Patents

分離膜およびその製造方法 Download PDF

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Publication number
WO2011118486A1
WO2011118486A1 PCT/JP2011/056341 JP2011056341W WO2011118486A1 WO 2011118486 A1 WO2011118486 A1 WO 2011118486A1 JP 2011056341 W JP2011056341 W JP 2011056341W WO 2011118486 A1 WO2011118486 A1 WO 2011118486A1
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Prior art keywords
separation
separation layer
separation membrane
base material
thickness
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PCT/JP2011/056341
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English (en)
French (fr)
Japanese (ja)
Inventor
龍也 市川
貞次郎 秦野
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東レ株式会社
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Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to EP11759292.3A priority Critical patent/EP2551010B1/de
Priority to US13/636,316 priority patent/US9617683B2/en
Priority to JP2011526349A priority patent/JP5733209B2/ja
Priority to CN201180011250.XA priority patent/CN102781559B/zh
Priority to KR1020127024530A priority patent/KR101810708B1/ko
Publication of WO2011118486A1 publication Critical patent/WO2011118486A1/ja

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0013—Casting processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0016—Coagulation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/06—Flat membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1213—Laminated layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1216—Three or more layers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/05—Cellulose or derivatives thereof
    • D06M15/07—Cellulose esters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59—Polyamides; Polyimides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/63—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing sulfur in the main chain, e.g. polysulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/23—Specific membrane protectors, e.g. sleeves or screens
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/42—Details of membrane preparation apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength

Definitions

  • the present invention relates to a separation membrane such as a reverse osmosis membrane, a microfiltration membrane, and an ultrafiltration membrane and a method for producing the same.
  • Separation membranes are used in various fields such as seawater desalination, water treatment such as water purification and wastewater treatment, medical fields such as blood purification, food industry, battery separators, electrical separators such as charged membranes and fuel cells. It's being used.
  • Such a separation membrane is generally composed of a base material (sheet) made of a woven fabric or a non-woven fabric and a separation layer having a separation function directly formed thereon.
  • JP 2007-283287A discloses a separation membrane in which a polyvinylidene fluoride-based separation layer is formed on a base material made of a polyester nonwoven fabric.
  • JP2003-245530A and JP09-313905A disclose a separation membrane in which a polysulfone-based separation layer is formed on a base material made of a polyester nonwoven fabric.
  • Such a separation membrane is obtained by applying a polymer solution for forming a separation layer to the surface of a long base material, and then allowing the base material coated with the polymer solution to pass through a coagulation and washing process to obtain the surface of the base material. It is manufactured by directly forming a separation layer. At this time, since the base material and the separation layer have different chemical compositions and different heat shrinkage rates, a phenomenon occurs in which both end portions in the width direction of the base material are curled.
  • FIG. 12 a shows a state immediately after a polymer solution that forms a separation layer of a separation membrane is applied on a long substrate 121 and a coating film 122 of the polymer solution is formed on the surface of the substrate 121.
  • FIG. 12a the left-right direction is the width direction of the base material 121, and the longitudinal direction of the base material 121 is a direction perpendicular to the paper surface.
  • the base material 121 to which the polymer solution has been applied is subsequently immersed in a coagulating liquid, and the coating film 122 of the polymer solution is coagulated.
  • the base material 121 on which the coating film 122 of the polymer solution is solidified is washed with water and washed to produce a separation membrane composed of the base material and the separation layer.
  • FIG. 12 b is a schematic cross-sectional view showing an initial state of occurrence of the curl 123 at both ends of the base material 121.
  • FIG. 12c is a schematic cross-sectional view showing a state of the rounded curl 124 formed by curling the generated curl 123 gradually and curling so that both ends of the base material 121 enter the inside of the curl.
  • FIG. 12 b is a schematic cross-sectional view showing an initial state of occurrence of the curl 123 at both ends of the base material 121.
  • FIG. 12c is a schematic cross-sectional view showing a state of the rounded curl 124 formed by curling the generated curl 123 gradually and curling so that both ends of the base material 121 enter the inside of the curl.
  • the present invention suppresses the occurrence of curling at both ends in the width direction of a long base material in the manufacturing process of the separation membrane found in the above prior art, and the separation membrane having substantially no curl and its manufacture
  • the purpose is to provide a method.
  • the separation membrane for achieving the above object is as follows.
  • a separation membrane comprising a long base material having fluid permeability and a separation layer formed on the surface of the base material, wherein the separation layer has a predetermined thickness portion having a predetermined thickness and a width of the predetermined thickness portion.
  • a thin portion having a thickness smaller than the predetermined thickness from the both ends in the direction, and the outer end in the width direction of each thin portion and the both ends in the width direction of the substrate.
  • a separation membrane having a separation layer absent portion in which only the base material is present and the separation layer is not present.
  • the base material is formed of a nonwoven fabric
  • the separation layer is formed of at least one of polysulfone, polyvinylidene fluoride, and cellulose acetate.
  • the separation membrane of this aspect is a separation membrane in which the separation layer is a single layer.
  • a separation membrane having a single separation layer is preferably used as an ultrafiltration membrane, a microfiltration membrane, a reverse osmosis membrane, or a nanofiltration membrane.
  • a second separation layer having a uniform thickness may be present on the surface of the separation layer.
  • the base material is formed of a nonwoven fabric
  • the separation layer is formed of polysulfone
  • the second separation layer is formed of polyamide.
  • the separation membrane of this embodiment is a composite separation membrane having a plurality of separation layers.
  • a separation membrane comprising a plurality of separation layers is preferably used as a reverse osmosis membrane or a nanofiltration membrane.
  • a protective layer having fluid permeability and having a uniform thickness may be present on the surface of the separation layer.
  • a fluid-permeable protective layer formed with a substantially uniform thickness may be present on the surface of the second separation layer.
  • the thickness of the thin portion may be substantially the same in the width direction, or may be inclined so as to become thinner toward the outer ends thereof, or a staircase The shape may be changed. Note that “substantially” when the thickness of the thin portion is substantially the same in the width direction means that the thickness may vary within a range of ⁇ 20% in the width direction.
  • the thickness of the thin portion is preferably 5 to 95% of the thickness of the predetermined thickness portion.
  • the width of the thin portion is preferably 0.1 to 10% of the width of the substrate.
  • the width of the separation layer absent portion is 0.1 to 10% of the width of the base material.
  • separation membranes may be manufactured and then wound into a roll so that the base material is located on the outside to form a separation membrane winding body. Most of the separation membranes are stored in the state of the separation membrane roll.
  • a separation membrane used for manufacturing a separation element using a separation membrane is prepared by cutting a separation membrane of a necessary length from a separation membrane drawn from a separation membrane winding body.
  • the manufacturing method of the separation membrane for achieving the above object is as follows.
  • a method for producing a separation membrane comprising a step, wherein, in the polymer solution coating step, the polymer solution is not applied to the surface of the substrate at both ends in the width direction of the substrate.
  • the separation layer formed in the separation layer forming step has a predetermined thickness using a coating bar having convex portions on the left and right ends of the surface in contact with the polymer solution as the coating bar.
  • the base has a predetermined thickness portion and a thin thickness portion having a thickness smaller than the thickness of the predetermined thickness portion between both ends of the predetermined thickness portion and each inner end of the polymer solution uncoated portion.
  • this method of manufacturing a separation membrane it is preferable to have a second separation layer formation step of forming a second separation layer with a uniform thickness on the surface of the separation layer formed in the separation layer formation step.
  • the separation membrane manufacturing method includes a protective layer forming step of forming a fluid-permeable protective layer with a uniform thickness on the surface of the second separation layer formed in the second separation layer forming step. It is preferable.
  • the height of the convex portion between the surface of the coating bar forming the predetermined thickness portion and the surface of the convex portion forming the thin thickness portion is: It is preferably 5 to 95% of the distance between the surface of the substrate and the surface of the coating bar forming the predetermined thickness portion.
  • the separation membrane includes a predetermined thickness portion where the polymer solution is applied with a predetermined thickness in a step in which the polymer solution forming the separation layer is applied to the surface of the substrate, and the predetermined thickness on both sides of the predetermined thickness portion.
  • the thin part to be applied with a thickness thinner than the thickness of the part is formed in the width direction of the base material, and the base material is exposed without the polymer solution being applied outside the part where the polymer solution is applied.
  • the base material to which the polymer solution is applied is introduced into a separation layer forming step for solidifying the polymer solution. Is done.
  • FIG. 1 is a schematic cross-sectional view of one embodiment of a separation membrane.
  • FIG. 2 is a schematic cross-sectional view of another embodiment of the separation membrane.
  • FIG. 3 is a schematic cross-sectional view of another embodiment of the separation membrane.
  • FIG. 4 is a schematic cross-sectional view of another embodiment of the separation membrane.
  • FIG. 5 is a schematic plan view of an example of a bar coater used in a polymer solution coating process in which a polymer solution is coated on the surface of a substrate.
  • 6 is a longitudinal sectional view taken along the line XX in FIG.
  • FIG. 7 is a schematic cross-sectional view illustrating a state in which the polymer solution is applied to the surface of the base material with a coating bar having convex portions at both ends shown in FIG.
  • FIG. 8 is a schematic cross-sectional view of the separation membrane produced in Comparative Example 1.
  • FIG. 9 is a schematic cross-sectional view of the separation membrane produced in Comparative Example 2.
  • FIG. 10 is a schematic cross-sectional view of the separation membrane produced in Comparative Example 3.
  • FIG. 11 is a schematic cross-sectional view illustrating a state in which a polymer solution is applied to the surface of a substrate with a coating bar that does not have convex portions at both ends.
  • FIG. 12 a is a schematic cross-sectional view illustrating the state of the base material immediately after the polymer solution is applied to the base material.
  • FIG. 12B is a schematic cross-sectional view for explaining the subsequent curl generation state of the substrate shown in FIG. 12A.
  • FIG. 12c is a schematic cross-sectional view for explaining a subsequent change state of curl generated in the base material shown in FIG. 12b.
  • FIG. 13 is a schematic cross-sectional view of an end portion of a base material for explaining a criterion for determining whether or not the curl is substantially generated on the base material.
  • FIG. 1 is a schematic cross-sectional view of an embodiment of a separation membrane manufactured without curling at both ends in the manufacturing process.
  • the separation membrane 1SM is composed of a long base material 1 having fluid permeability and a separation layer 2 formed on the surface of the base material 1.
  • the separation layer 2 has a predetermined thickness portion 12a having a predetermined thickness necessary for fulfilling a separation function, and a thin thickness having a thickness smaller than a predetermined thickness located on both sides from both ends in the width direction of the predetermined thickness portion 12a.
  • the separation membrane 1SM has only the base material 1 between the outer end in the width direction of each thin thickness part 12b and both side ends in the width direction of the base material 1, and the separation layer 2 is It has a separation layer absent portion 1c that does not exist.
  • the separation layer absent portion 1c can also be referred to as a substrate exposed portion 1c.
  • the base material 1 has a width a in the width direction.
  • the thin portion 12 b existing at one end of the separation layer 2 has a width b 1 in the width direction of the substrate 1.
  • the thin portion 12 b existing at the other end of the separation layer 2 has a width b 2 in the width direction of the substrate 1.
  • the separation layer absent portion 1 c present at one end of the substrate 1 has a width c 1 in the width direction of the substrate 1.
  • the separation layer absent portion 1 c present at the other end of the substrate 1 has a width c 2 in the width direction of the substrate 1.
  • the contour line drawn in the cross section by the surface of the separation layer 2 from the end in the width direction of the surface of the predetermined thickness portion 12a to the surface of the substrate 1 through the surface of the thin thickness portion 12b may be a step-like line segment. Alternatively, it may be a line segment composed of continuous straight lines or curves.
  • the contour is stepped, and the thickness value of the thin portion 12b is the same over the entire widths b1 and b2 of the thin portion 12b, that is, the surface of the thin portion 12b is flat.
  • a separation membrane 1SM is shown.
  • the step-like contour line may be changed into a plurality of steps.
  • the separation layer 2 of the separation membrane 1SM in FIG. 1 is formed as a single layer made of a material having a separation function formed on the surface of the substrate 1. This single layer may be referred to as an asymmetric membrane.
  • FIG. 2 is a schematic cross-sectional view of another embodiment of the separation membrane.
  • the contour line drawn on the cross section of the surface of the separation layer 2 from the end of the predetermined thickness portion 12a through the thin thickness portion 22b to the surface of the substrate 1 is a line segment composed of an inclined straight line.
  • the other points of the separation membrane 2SM are the same as those of the separation membrane 1SM of FIG. Therefore, in FIG. 2, the same reference numerals as in FIG. 1 are used for the same portions as in FIG.
  • FIG. 3 is a schematic cross-sectional view of still another embodiment of the separation membrane.
  • the separation membrane 3SM includes a long base material 1 having fluid permeability and a separation layer 32 formed on the surface of the base material 1.
  • the separation layer 32 includes a first separation layer 3 and a second separation layer 4 formed on the surface of the first separation layer 3.
  • the cross-sectional shape of the first separation layer 3 is the same as the cross-sectional shape of the separation layer 2 shown in FIG. Accordingly, the first separation layer 3 is identical in shape to the separation layer 2 shown in FIG.
  • the first separation layer 3 has a predetermined thickness portion 32a and a thin thickness portion 32b as in the case of the separation layer 2 of FIG.
  • the second separation layer 4 is a layer formed on the surface of the first separation layer 3 and having a separation function different from the separation function of the first separation layer 3.
  • the second separation layer 4 is formed by various methods.
  • the second separation layer forming material is applied to the surface of the first separation layer 3 with a uniform thickness and solidified, or the second separation layer is formed on the surface of the first separation layer 3. Examples thereof include a method of forming a material for formation by interfacial polymerization.
  • the separation layer 32 of the separation membrane 3SM in FIG. 3 includes a plurality of layers of a material having a separation function formed on the surface of the substrate 1 and a layer of a material having a separation function different from that of the material formed thereon. It is formed with.
  • This plurality of layers may be referred to as a composite membrane.
  • the difference between the separation membrane 3SM shown in FIG. 3 and the separation membrane 1SM shown in FIG. 1 is that the separation layer 2 in FIG. 1 is composed of a single layer of a material having a separation function, whereas the separation layer 32 in FIG. , The separation function is composed of a plurality of layers of different materials.
  • the other points of the separation membrane 3SM are the same as those of the separation membrane 1SM of FIG. Therefore, in FIG. 3, the same reference numerals as those in FIG. 1 are used for the same portions as in FIG.
  • FIG. 4 is a schematic cross-sectional view of still another embodiment of the separation membrane.
  • the difference between the separation membrane 4SM shown in FIG. 4 and the separation membrane 3SM shown in FIG. The contour line drawn on the cross section of the surface of the separation layer 32 from the end of the predetermined thickness portion 32a through the thin thickness portion 42b to the surface of the substrate 1 is a line segment composed of an inclined straight line.
  • the other points of the separation membrane 4SM are the same as the separation membrane 3SM of FIG. Therefore, in FIG. 4, the same reference numerals as in FIG. 3 are used for the same portions as in FIG.
  • the protective layer which has the fluid permeability of uniform thickness may be formed in the surface of the separation layer 32 shown in FIG. 3, or the separation layer 32 shown in FIG.
  • This protective layer is formed of, for example, a material having a function of reducing contamination of each separation layer. As a result, the fouling resistance of the separation membrane is improved.
  • FIG. 5 is a schematic plan view of the bar coater 50 used in the manufacturing process of the separation membrane 1SM and the vicinity thereof.
  • 6 is a longitudinal sectional view taken along the line XX in FIG.
  • FIG. 7 is a schematic cross-sectional view for explaining the formation state of the separation layer on the surface of the base material by the coating bar provided in the bar coater 50.
  • the bar coater 50 is opposed to the backup roll 53, the coating bar 54 provided facing the surface of the backup roll 53, the surface of the backup roll 53 and the surface of the coating bar 54, and is spaced from side to side.
  • the side plate 55 is located on the side.
  • the coating bar 54 may be a rotating round bar having a circular cross section, a non-rotating round bar, an edged bar called a roll knife, or a blade type. Further, the surface may have a periodic depression.
  • the long base material 1 having fluid permeability is continuously conveyed by a rotating base material supply roll 52 and supplied to the bar coater 50.
  • the back surface of the substrate 1 contacts the surface of the backup roll 53 and is further conveyed.
  • a separation layer forming solution 56 to be a separation layer later is supplied to the space surrounded by the side plate 55, the coating bar 54 and the surface of the substrate 1.
  • a bank of solution 56a is formed.
  • a separation layer forming solution 56 to be a separation layer later is applied to the surface of the base material 1 with a predetermined thickness by the coating bar 54.
  • the coating bar 54 has a predetermined diameter portion 54a having a predetermined diameter, and convex portions 54b having diameters larger than the diameter of the predetermined diameter portion 54a at both ends thereof.
  • the convex portion 54b can be obtained by processing a conventional coating bar so that a thick portion is formed. For example, the shape of the thin portion at the positions corresponding to the thin portions (the thin portion 12b in FIG. 1 and the thin portion 22b in FIG. 2) on the surfaces of both ends of a conventionally known round bar coating bar.
  • a desired convex portion can be formed by adhering a thin film having a thickness that enables formation of the above.
  • the separation layer 2 having the shape shown in FIG. 1 is formed. That is, the predetermined thickness portion 12a is formed by the predetermined diameter portion 54a, and the thin thickness portion 12b is formed by the convex portion 54b.
  • This state is depicted as widths b1, b2, c1, and c2 in FIG. 5, but in fact, in the state of FIG. 5, the solution 56 for forming the separation layer is not yet solidified. Is not exactly the same as The widths b1, b2, c1 and c2 in FIG. 5 are for easy understanding.
  • the separation membrane is formed by forming a separation layer made of a material having a separation function on the surface of a long base material having fluid permeability.
  • the substrate has a function as a support for the separation layer and a function for improving the strength of the separation membrane.
  • the separation layer penetrates to a certain depth inside the base material, or penetrates to the back surface of the base material, and is formed on the surface of the base material, so that the separation layer and the base material are firmly integrated. Therefore, it is preferable.
  • the base material is made of, for example, polyester, polypropylene, polyethylene, or polyamide fiber, for example, woven fabric, non-woven fabric, or net. From the viewpoint of formability of the separation layer on the surface of the base material (film forming property) or cost, a nonwoven fabric is preferably used as the base material.
  • Nonwoven fabrics can be produced, for example, by forming a short fiber and a binder fiber, which are uniformly dispersed in water, into a sheet using a circular net or a long net, and then drying the paper sheet. . By fusing and processing the sheet thus produced between two heated rolls, the fluff of the produced nonwoven fabric can be reduced or the mechanical properties can be improved.
  • the separation layer is a membrane having a function of separating the target component from the stock solution.
  • the separation layer may be composed of a single layer of a material having a separation function, or may be composed of a plurality of layers of materials having different separation functions.
  • a separation layer composed of a single layer may be referred to as an asymmetric membrane, and a separation layer composed of a plurality of layers may be referred to as a composite membrane.
  • the asymmetric membrane is formed by casting a film-forming solution for forming an asymmetric membrane on the surface of the substrate, forming a film of the film-forming solution on the surface of the substrate, and then forming the film-forming solution on the surface of the substrate. This film is formed by solidifying the film.
  • the formed asymmetric membrane is a microporous material.
  • polymer material used as the film-forming solution examples include polyacrylonitrile, polysulfone, polyethersulfone, polyphenylenesulfone, polyphenylenesulfidesulfone, polyvinylidene fluoride, cellulose acetate, polyethylene, and polypropylene.
  • the thickness of the microporous material varies depending on the application and the like, but is generally about 20 to 200 ⁇ m.
  • the composite membrane is composed of a separation layer (first separation layer) made of a microporous material and a second separation layer formed on the separation layer to exhibit a main separation function.
  • a separation layer (first separation layer) made of a microporous material is first formed on the surface of the substrate, and then a second separation function that provides a main separation function on the surface of the separation layer made of the microporous material. It is formed by forming a separation layer.
  • the separation layer made of the microporous material can be formed in the same manner as the separation layer made of the microporous material in the asymmetric membrane.
  • polysulfone examples include polysulfone, polyethersulfone, polyphenylene sulfide sulfone, polyphenylene sulfone, polyphenylene oxide, polyphenylene sulfide, polyacrylonitrile, polyamide, polyester, polyimide, or acetic acid.
  • cellulose There is cellulose.
  • Examples of the polymer material for forming the second separation layer that provides the main separation function include polyamide and polyimide. A film formed from these is usually called a semipermeable membrane.
  • the thickness of the separation layer (first separation layer) made of a microporous material varies depending on the application and the like, but generally may be about 20 to 200 ⁇ m.
  • the advantage of the composite membrane is that the performance of the separation membrane can be variously adjusted by combining various membranes.
  • the separation membrane can be used as an ultrafiltration membrane, a microfiltration membrane, a reverse osmosis membrane, or a nanofiltration membrane.
  • the ultrafiltration membrane and the microfiltration membrane may have a separation layer formed using, for example, a polysulfone polymer such as polysulfone having alkali resistance, or a fluorine polymer such as polyvinylidene fluoride having high chemical resistance. preferable.
  • the nanofiltration membrane and reverse osmosis membrane preferably have a second separation layer formed using, for example, cellulose acetate or polyamide that is excellent in hydrolysis resistance, chemical resistance, and pressure resistance.
  • a separation membrane having a high salt rejection rate and a high water production amount it is preferable to form the semipermeable membrane in the composite membrane with an aromatic polyamide.
  • the protective layer may be formed. good.
  • a coating film aiming at resistance to fouling, for example, there is a coating film of a hydrophilic polymer such as polyvinyl alcohol.
  • the materials for forming the base material, the separation layer, the second separation layer, and the protective layer are known in the past.
  • the features of the separation membrane and the method of manufacturing the separation membrane proposed in this specification are the following technical requirements.
  • the separation layer formed on the surface of the base material has a predetermined thickness portion having a predetermined thickness and a thin thickness having a thickness smaller than a predetermined thickness located on both sides from both ends in the width direction of the predetermined thickness portion.
  • the base material is between the outer edge in the width direction of each thin-thickness part and both side edges in the width direction of the base material. It is a separation membrane which has a part (base material exposure part).
  • FIG. 13 is a schematic cross-sectional view of an end portion of a base material for explaining a criterion for determining whether or not the curl is substantially generated on the base material.
  • the separation membrane SM is placed on the upper surface of the determination base MP such that the upper surface of the determination base MP and the back surface of the base material of the separation membrane SM face each other. After the placement, when curl is present at the side end portion of the base material of the separation membrane SM, the end portion Be of the base material is lifted upward from the upper surface of the determination base MP.
  • the distance between the position Bep at which the perpendicular drawn from the end portion Be of the base material intersects the upper surface of the determination base MP and the end portion Be of the base material is defined as the height H.
  • a position where the base material starts to move away from the upper surface of the determination base MP is defined as a curl start position Cs, and a length from the curl start position Cs to the end Be of the base material along the base material is defined as a curl length L.
  • Whether the curl is substantially generated on the base material is determined based on the curl length L and the lifting height H. That is, when the curl length L is less than 60 mm and the lifting height H is less than 55 mm, it is determined that the separation membrane SM has no curl. In other words, it is determined that such a curl is substantially free of curl. On the other hand, when the curl length L is 60 mm or more and the lifting height H is 55 mm or more, it is determined that the separation membrane SM is curled.
  • the predetermined thickness of the separation layer refers to the thickness of the separation layer necessary for exhibiting the intended separation function.
  • the thickness of the separation layer formed by solidifying the coating layer of the polymer solution decreases, the thermal shrinkage that occurs during solidification or cleaning decreases, and the pulling force on the substrate decreases accordingly. Utilizing this phenomenon, curling at both ends of the substrate is suppressed. That is, a thin portion having a thickness smaller than a predetermined thickness of the separation layer is present at both end portions in the width direction of the separation layer, and the force for pulling the base material at both ends of the thin portion is reduced.
  • the thickness of the thin portion is preferably inclined and / or stepped so as to become thinner toward the outside.
  • the width b1, b2 (see FIGS. 1 to 4) of the thin portion is preferably wide, but if it is too wide, the separation function is exhibited.
  • the effective membrane area is reduced.
  • the widths b1 and b2 of the thin portion are preferably 0.1 to 10%, more preferably 0.1 to 5% of the width a of the substrate.
  • the thickness of the thin portion is preferably 5 to 95% of the thickness of the predetermined thickness portion, more preferably 30 to 80%, and more preferably 45 to 65%.
  • the thickness of the thin portion may be about 20 to 40 ⁇ m.
  • the thickness of the thin portion is an average value of values obtained by measuring the thickness of the thin portion over its width. That is, the thickness of the thin portion is the average value of 20 measurement values obtained by measurement using a microscope at 20 measurement positions at equal intervals including both ends over the width of the thin portion. .
  • the thickness of the predetermined thickness portion is an average value of values obtained by measuring the thickness of the separation layer excluding the thin thickness portion over the width. That is, the thickness of the predetermined thickness portion is an average value of 20 measurement values obtained by measuring with a thickness measuring instrument at 20 measurement positions at equal intervals across the width of the predetermined thickness portion. It is.
  • Providing the base material exposed portion outside the thin thickness portion means providing a portion where the polymer solution is not applied at all at the outermost end of the base material.
  • This exposed substrate portion is effective in preventing curling of the separation membrane without curling during the coagulation of the polymer solution and the cleaning of the separation membrane.
  • the base material exposed part is provided, if there is no thin part, the base material exposed part is drawn in by the curl generated at both end portions of the separation layer and enters the inside of the curl, thus preventing curling. It becomes difficult.
  • the widths c1 and c2 (see FIGS. 1 to 4) of the base exposed portion are preferably 0.1 to 10%, more preferably 0.1 to 5% of the base width a.
  • a wider substrate exposed portion is preferable from the viewpoint of curling prevention, but if it exceeds 10% of the width a of the substrate, the effective membrane area of the separation function decreases.
  • the height of the convex portion 54b from the surface to which the predetermined thickness portion of the coating bar is applied is between the position of the surface of the base material and the position of the surface to which the predetermined thickness portion of the coating bar is applied (the surface excluding the convex portion).
  • the distance is preferably 5 to 95%, more preferably 30 to 80%.
  • the height of the convex portion functions to form the thickness of the thin portion.
  • the thin portion for example, other means for reducing the coating amount of the polymer solution only in the portion where the thin portion is formed may be employed.
  • a polyester nonwoven fabric (basis weight 60 g / m 2 , thickness 80 ⁇ m, width 1000 mm) was used as the substrate.
  • Polysulfone (Udel (registered trademark) P-3500 of Solvay Advanced Polymers Co., Ltd.) was used as a material for forming the separation layer.
  • a polysulfone solution (concentration 16% by weight, temperature 20 ° C.) obtained by dissolving this polysulfone in dimethylformamide was used as a polymer solution for forming a separation layer. This polymer solution was applied to the front side of the nonwoven fabric except for a certain width at both left and right ends. At this time, a bar coater (see FIG.
  • a coating bar having a stepped surface provided with convex portions (large diameter portions) having a height of 50 ⁇ m at both ends is arranged on the nonwoven fabric surface to which the polymer solution is applied.
  • the polymer solution is applied to the nonwoven fabric surface so that a predetermined thickness portion is formed, and a predetermined thin thickness portion is formed at both right and left end portions in the width direction by the convex portion (large diameter portion) of the coating bar. It was applied as follows. The back surface of the nonwoven fabric was supported by a backup roll over its entire width.
  • the non-woven fabric coated with the polymer solution is immersed in pure water at 20 ° C. 0.5 seconds after coating to solidify the polysulfone, and a microporous polysulfone separating functional layer (thickness of a predetermined thickness portion: thickness: A separation membrane having a thickness of 50 ⁇ m and a thickness of 30 ⁇ m of the thin part was manufactured.
  • the obtained separation membrane was washed with a water washing tank to remove the solvent remaining on the separation membrane, and then the separation membrane was wound up by a winding device.
  • the left and right ends of the separation layer in the produced separation membrane had the shape shown in FIG. Table 1 shows the widths c1 and c2 of the substrate exposed portion, the widths b1 and b2 of the thin portion, and the thickness of the thin portion.
  • the curl mentioned here means a curl that the film formation must be interrupted (the same applies to the following examples and comparative examples).
  • the right side and the left side in Table 1 mean the right end and the left end with respect to the running direction of the substrate.
  • Example 1 is the same as Example 1 except that a round bar coating bar having no convex portions is used on the contact surface with the polymer solution and the polymer solution is applied to the left and right ends of the substrate.
  • a separation membrane was produced.
  • FIG. 8 is a schematic cross-sectional view of the manufactured separation membrane.
  • the separation layer 82 of the manufactured separation membrane 8SM is formed across the left and right ends of the substrate 1, and the substrate 1 has no substrate exposed portion.
  • the thickness of the separation layer 82 was the same up to the left and right ends of the substrate 1 and there was no thin portion.
  • Example 1 a separation membrane was produced in the same manner as in Example 1 except that the polymer solution was applied to both ends of the substrate.
  • FIG. 9 is a schematic cross-sectional view of the manufactured separation membrane.
  • the separation layer 92 of the manufactured separation membrane 9SM is formed over the left and right ends of the substrate 1, and the substrate 1 has no substrate exposed portion.
  • the widths b1 and b2 of the thin part and the thickness of the thin part were as shown in Table 1.
  • FIG. 11 is a schematic cross-sectional view illustrating a state in which a polymer solution is applied to the surface of a substrate with a coating bar having no step.
  • the polymer solution 1156 was applied to the surface of the substrate 1 with a coating bar 1154 having no step attached to the bar coater 1150.
  • the back surface of the substrate 1 was supported by a backup roll.
  • FIG. 10 is a schematic cross-sectional view of the manufactured separation membrane.
  • the manufactured separation membrane 10SM has a substrate exposed portion between the left and right ends of the separation layer 102 and the left and right ends of the substrate 1.
  • Table 1 shows the widths c1 and c2 of the substrate exposed portions at the left and right ends of the separation membrane 10SM.
  • the thickness of the separation layer 102 was the same up to the left and right ends of the separation membrane 10SM, and there was no thin portion. When the presence or absence of curling at the left and right ends of the separation membrane 10SM was determined, it was apparent that curling had occurred, and the film formation had to be interrupted temporarily.
  • the separation membrane produced in Example 1 was immersed in a 2% by weight aqueous solution of m-phenylenediamine for 1 minute. After removing the excess amine aqueous solution from the surface of the polysulfone membrane forming the separation layer (first separation layer), the solution was dried with a hot air dryer at 80 ° C. for 1 minute to concentrate the aqueous solution. Subsequently, a 0.1% by weight n-decane solution of trimesic acid chloride was coated on the surface of the polysulfone membrane so that the surface was completely wetted, and then allowed to stand for 1 minute, thereby reverse osmosis on the polysulfone membrane. A polyamide separation layer (second separation layer) having a membrane separation function was formed to produce a separation membrane.
  • the left and right ends of the separation layer in the produced separation membrane had the shape shown in FIG. Table 1 shows the widths c1 and c2 of the exposed part of the substrate, the widths b1 and b2 of the thin part, and the thickness of the thin part.
  • Example 1 a convex part having a stepped surface on the surface of the coating bar was changed to a convex part having a slope surface, and a separation membrane having a shape shown in FIG. 2 was produced.
  • the results in this case are as shown in Table 1. The occurrence of curling could not be confirmed.
  • the separation membrane of the present invention and the production method thereof are used for separation membranes used in reverse osmosis membranes, microfiltration membranes, ultrafiltration membranes and the like, and their production.
  • This separation membrane is used, for example, in the field of water treatment such as seawater desalination, water purification and wastewater treatment.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
PCT/JP2011/056341 2010-03-23 2011-03-17 分離膜およびその製造方法 WO2011118486A1 (ja)

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EP11759292.3A EP2551010B1 (de) 2010-03-23 2011-03-17 Trennmembran und verfahren zu ihrer herstellung
US13/636,316 US9617683B2 (en) 2010-03-23 2011-03-17 Separation membrane and method for producing same
JP2011526349A JP5733209B2 (ja) 2010-03-23 2011-03-17 分離膜およびその製造方法
CN201180011250.XA CN102781559B (zh) 2010-03-23 2011-03-17 分离膜及其制造方法
KR1020127024530A KR101810708B1 (ko) 2010-03-23 2011-03-17 분리막 및 그의 제조 방법

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014144393A (ja) * 2013-01-28 2014-08-14 Nof Corp 多孔質濾過膜用ファウリング抑制剤組成物、並びに多孔質濾過膜及びその製造方法
JP2014161847A (ja) * 2013-02-21 2014-09-08 Korea Institute Of Science And Technology 有機単量体間の架橋を利用した多層薄膜基盤の逆浸透分離膜及びその製造方法
WO2015068657A1 (ja) * 2013-11-05 2015-05-14 日東電工株式会社 複合半透膜
KR20170095835A (ko) 2014-12-16 2017-08-23 닛토덴코 가부시키가이샤 다공성 지지체, 복합 반투막, 및 스파이럴형 분리막 엘리먼트

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015064720A1 (ja) 2013-10-30 2015-05-07 東レ株式会社 分離膜、シート流路材および分離膜エレメント
GB2531001B (en) * 2014-10-06 2019-06-05 Canon Kk Method and apparatus for vector encoding in video coding and decoding
JP6747926B2 (ja) * 2015-09-30 2020-08-26 日東電工株式会社 スパイラル型分離膜エレメントの製造方法
GB2587786B (en) 2019-07-11 2022-10-19 Crafters Companion Ltd Improved crafting dies
KR20220029972A (ko) 2020-09-02 2022-03-10 김진용 인공지능을 이용한 지원 대상자 건강관리상품 추천 시스템 및 방법

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0931390A (ja) 1995-07-18 1997-02-04 Sequa Corp 水性インキ
JPH09313905A (ja) 1996-05-23 1997-12-09 Nitto Denko Corp ポリスルホン多孔質分離膜
JP2000042384A (ja) * 1998-07-27 2000-02-15 Nitto Denko Corp シート状分離膜の製造法
JP2003245530A (ja) 2001-12-10 2003-09-02 Toray Ind Inc 分離膜
WO2006068100A1 (ja) * 2004-12-21 2006-06-29 Asahi Kasei Fibers Corporation 分離膜支持体
JP2007283287A (ja) 2006-03-24 2007-11-01 Toray Ind Inc ポリフッ化ビニリデン系多孔質分離膜
JP2007289937A (ja) * 2006-03-27 2007-11-08 Fujifilm Corp 微孔性膜の製造方法及び装置
JP2007289935A (ja) * 2006-03-27 2007-11-08 Fujifilm Corp 微孔性膜の製造方法及び装置
JP2008119680A (ja) * 2006-10-20 2008-05-29 Toray Ind Inc 膜分離エレメント及び膜分離モジュール

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4756835A (en) * 1986-08-29 1988-07-12 Advanced Polymer Technology, Inc. Permeable membranes having high flux-density and low fouling-propensity
SE470534B (sv) 1992-11-27 1994-07-25 Electrolux Ab Förfarande för framställning av ett membranfilter samt membranfilter för fluidrenare
JP3028900B2 (ja) * 1993-07-16 2000-04-04 株式会社クボタ 膜エレメントの製造方法
TW255835B (en) * 1994-01-07 1995-09-01 Kubota Kk Filtration membrane module
US6153098A (en) * 1997-09-03 2000-11-28 Filtration Systems, Inc. Spiral wound filter with central barrier
AU2001219539A1 (en) * 2000-09-05 2002-03-22 Wesley L. Bradford Reverse osmosis membrane and process for making same
US6596112B1 (en) * 2000-10-20 2003-07-22 Pall Corporation Laminates of asymmetric membranes
AU2002316608A1 (en) * 2001-07-06 2003-01-21 Millipore Corporation Satterned composite membrane and stenciling method for the manufacture thereof
US7959780B2 (en) * 2004-07-26 2011-06-14 Emporia Capital Funding Llc Textured ion exchange membranes
US7780833B2 (en) * 2005-07-26 2010-08-24 John Hawkins Electrochemical ion exchange with textured membranes and cartridge
DE102006044635B4 (de) * 2006-09-19 2008-11-06 Gkss-Forschungszentrum Geesthacht Gmbh Gastrenn-Membran
CN101579604A (zh) * 2009-06-19 2009-11-18 南昌航空大学 一种管式复合中空纤维膜的制备方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0931390A (ja) 1995-07-18 1997-02-04 Sequa Corp 水性インキ
JPH09313905A (ja) 1996-05-23 1997-12-09 Nitto Denko Corp ポリスルホン多孔質分離膜
JP2000042384A (ja) * 1998-07-27 2000-02-15 Nitto Denko Corp シート状分離膜の製造法
JP2003245530A (ja) 2001-12-10 2003-09-02 Toray Ind Inc 分離膜
WO2006068100A1 (ja) * 2004-12-21 2006-06-29 Asahi Kasei Fibers Corporation 分離膜支持体
JP2007283287A (ja) 2006-03-24 2007-11-01 Toray Ind Inc ポリフッ化ビニリデン系多孔質分離膜
JP2007289937A (ja) * 2006-03-27 2007-11-08 Fujifilm Corp 微孔性膜の製造方法及び装置
JP2007289935A (ja) * 2006-03-27 2007-11-08 Fujifilm Corp 微孔性膜の製造方法及び装置
JP2008119680A (ja) * 2006-10-20 2008-05-29 Toray Ind Inc 膜分離エレメント及び膜分離モジュール

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2551010A4

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014144393A (ja) * 2013-01-28 2014-08-14 Nof Corp 多孔質濾過膜用ファウリング抑制剤組成物、並びに多孔質濾過膜及びその製造方法
JP2014161847A (ja) * 2013-02-21 2014-09-08 Korea Institute Of Science And Technology 有機単量体間の架橋を利用した多層薄膜基盤の逆浸透分離膜及びその製造方法
WO2015068657A1 (ja) * 2013-11-05 2015-05-14 日東電工株式会社 複合半透膜
CN105705222A (zh) * 2013-11-05 2016-06-22 日东电工株式会社 复合半透膜
US10682615B2 (en) 2013-11-05 2020-06-16 Nitto Denko Corporation Composite semi-permeable membrane
CN105705222B (zh) * 2013-11-05 2021-02-02 日东电工株式会社 复合半透膜
KR20170095835A (ko) 2014-12-16 2017-08-23 닛토덴코 가부시키가이샤 다공성 지지체, 복합 반투막, 및 스파이럴형 분리막 엘리먼트

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CN102781559A (zh) 2012-11-14
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US9617683B2 (en) 2017-04-11
JPWO2011118486A1 (ja) 2013-07-04
JP5733209B2 (ja) 2015-06-10
EP2551010A4 (de) 2014-01-01
EP2551010A1 (de) 2013-01-30
EP2551010B1 (de) 2018-10-10
KR101810708B1 (ko) 2017-12-19
CN102781559B (zh) 2014-12-17

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